Brombutadiynyl-triethyl-silan | 55552-44-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: Brombutadiynyl-triethyl-silan
• 英文别名: 4-bromobuta-1,3-diynyl(triethyl)silane
• CAS: 55552-44-8
• 化学式: C₁₀H₁₅BrSi
• 分子量: 243.219
• InChiKey: JRZXLWHLRBQWGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  12.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  、 Brombutadiynyl-triethyl-silan 在 copper(l) iodide 、 正丁基锂 、 乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以44%的产率得到
  参考文献：
  名称：

  Toward Metal-Capped One-Dimensional Carbon Allotropes:  Wirelike C₆−C₂₀ Polyynediyl Chains That Span Two Redox-Active (η⁵-C₅Me₅)Re(NO)(PPh₃) Endgroups

  摘要：

  Reaction of the butadiynyl complex (eta(5)-C5Me5)Re(No)(PPh3)(C drop CC drop CH) (ReC4H) with Cu(OAc)(2) (pyridine, 80 degrees C) gives the mu-octatetraynediyl complex ReC8Re (70%). Analogous cross-coupling of ReC4H and ReC2H gives (after chromatography) ReC4Re (14%), ReC6Re (44%), and ReC8Re (15%). Longer sp carbon chains are accessed by reactions of ReC4H with n-BuLi and CuI, which give ReC4Cu. This isolable species is treated in situ with BrC drop CSiEt3 or BrC drop CC drop CSiMe3 (excess EtNH2, THF) to give ReC6SiEt3 or ReC8SiMe3 (84-77%). Desilylations (wet n-Bu4N+F-) yield ReC6H or ReC8H (88-73%). Then Cu(OAc)(2) (pyridine, 50 degrees C) gives ReC12Re or ReC16Re (71-67%). The former is also available from ReC4Cu and BrC drop CC drop CBr (45%), and ReC10Re can be accessed by cross-coupling. ReC6H and ReC8H are similarly converted to ReC10SiR3 (R = Me, Et; 51-26%) and ReC12SiMe3 (43%). Desilylation of ReC10SiR3 gives labile ReC10H, but only black powder is obtained from ReC12SiMe3. In situ coupling of ReC10H gives ReC20Re (52-34%), which unlike lower homologues is not obtained in analytically pure form. The effects of chain length upon visible spectra (progressively red-shifted and more intense bands; epsilon > 190 000 M-1 cm(-1)), IR/ Raman nu(C drop C) patterns (progressively more bands),C-13 NMR chemical shifts (asymptotic limit of 64-67 ppm for ReC drop C((C) under bar drop (C) under bar)(n)), cyclic voltammetry (decreased reversibility of two oxidations; a gradual shift of the first to thermodynamically less favorable potentials, so that only a single oxidation is observed for ReC20Re), and thermal stabilities (solid-state decompositions at 155 degrees C, ReC20Re, and 178-217 degrees C, lower homologues) are studied in detail.

  DOI：

  10.1021/ja992747z
• 作为产物：
  描述：

  1-Tri-n-butylstannyl-4-triethylsilylbutadiyne 在 溴 作用下， 生成 Brombutadiynyl-triethyl-silan
  参考文献：
  名称：

  Bromo- and lodo-butadiynyl(triethyl)silane: Reagents for Introducing a Protected Diacetylene Group in Cadiot-Chodkiewicz Reactions

  摘要：

  DOI：

  10.1055/s-1974-23472

文献信息

• A Step-Growth Approach to Metal-Capped One-Dimensional Carbon Allotropes: Syntheses of C12, C16, and C20μ-Polyynediyl Complexes
  作者：Tamás Bartik、Berit Bartik、Monika Brady、Roman Dembinski、J. A. Gladysz

  DOI：10.1002/anie.199604141

  日期：1996.3.1